JP2008292677A - Reactive resin composition, color filter, and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reactive resin composition capable of forming a rib or a spacer into a desired shape and superior in electric characteristics such as voltage holding rate, residual electric potential, and electric capacity, and to solve the problems such as uneven display or after images by preventing adverse effect on a liquid crystal layer when the rib or the spacer of an LCD is formed using the same. <P>SOLUTION: The reactive resin composition for forming liquid crystal orientation control protrusion, for forming the spacer, or for simultaneously forming the spacer and the liquid crystal orientation control protrusion includes, as constituent components, (A) and (B) as described below: (A) a resin having a condensate of a biphenyl compound and phenols at a skeleton; and (B) a photopolymerization initiator and/or a photoacid generator. A color filter and an image display device include the liquid crystal orientation control protrusion and/or the spacer formed by using the reactive resin composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a reactive resin composition for forming a liquid crystal alignment control protrusion, for forming a spacer, or for simultaneously forming a spacer and a liquid crystal alignment control protrusion, and in particular, a vertical alignment type for a liquid crystal display (LCD). The present invention relates to a reactive resin composition used for forming liquid crystal alignment control protrusions (ribs) and / or spacers of liquid crystal.
The present invention also relates to a color filter and an image display device having liquid crystal alignment control protrusions and / or spacers formed using this reactive resin composition.

  LCD utilizes the property that the arrangement of liquid crystal molecules is switched by turning on and off the voltage to the liquid crystal. On the other hand, each member forming the LCD cell is often formed by using a reactive resin composition typified by photolithography, and it is easy to form a fine structure with respect to a substrate for a large screen. From the reason that this treatment is easy, the application range of the reactive resin composition tends to be further expanded in the future.

  However, in an LCD using a reactive resin composition, the voltage applied to the liquid crystal may not be maintained due to the electrical characteristics of the reactive resin composition itself and the influence of impurities contained in the reactive resin composition. Even if the power is turned off, the electric potential remains, causing problems such as display unevenness and afterimage. In particular, the effect is great in ribs and spacers closer to the liquid crystal layer.

The reactive resin composition of the present invention comprises (A) and (B) described later as constituent components, and is particularly characterized by having the component (A). The resin itself having a skeleton of a condensate of a biphenyl compound and a phenol is described in JP-A-2001-329051. In Japanese Patent Application Laid-Open No. 2001-329051, this resin is used as a curing agent for epoxy resins, and its application fields include electric / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resists, optical materials. Are mainly used as a semiconductor sealing material.
JP 2001-329051 A

  The present invention has been made in view of the above-described conventional circumstances, and is capable of forming ribs and spacers in a preferable shape, and is a reactive resin excellent in electric characteristics such as voltage holding ratio, residual potential, and electric capacity. When a composition is provided and an LCD rib or spacer is formed using the composition, problems such as display unevenness and afterimage are improved by not adversely affecting the liquid crystal layer.

As a result of intensive studies on the above problems, the present inventor has found that the above problems can be solved by using a reactive resin composition containing the following (A) and (B) as constituent components.
Accordingly, the gist of the present invention is as follows.

[1] A reactive resin composition for forming liquid crystal alignment control protrusions and / or spacers, or for simultaneously forming liquid crystal alignment control protrusions and spacers, and comprising the following components (A) and (B): A reactive resin composition comprising:
(A) Resin having a skeleton of a condensate of a biphenyl compound and phenols (B) Photopolymerization initiator and / or photoacid generator

（式（１）中、Ｘは、水素原子、或いはカルボキシル基及び／又は水酸基を有しさらにその他の置換基を有していても良い炭化水素基であり、複数のＸは互いに同一であっても良く、異なっていても良い。ｎは平均値を表し１．２〜７である。また、式（１）中のベンゼン環は表記していない置換基を有していても良い。） [2] A reactive resin composition for forming liquid crystal alignment control protrusions and / or spacers, or for simultaneously forming liquid crystal alignment control protrusions and spacers, wherein the following (A) and (B) are constituent components A reactive resin composition comprising:
(A) Resin having a carboxyl group and / or a hydroxyl group represented by the following formula (1) (B) Photopolymerization initiator and / or photoacid generator

(In the formula (1), X is a hydrogen atom or a hydrocarbon group having a carboxyl group and / or a hydroxyl group and further having another substituent, and a plurality of Xs are the same as each other. (N represents an average value and is 1.2 to 7. In addition, the benzene ring in formula (1) may have a substituent which is not shown).

（式（２）中、ｎは式（１）におけると同義である。また、式（２）中のベンゼン環は表記していない置換基を有していても良い。） [3] The reactive resin composition according to [2], wherein the component (A) is a novolak resin represented by the following formula (2).

(In formula (2), n has the same meaning as in formula (1). Moreover, the benzene ring in formula (2) may have a substituent not shown.)

（式（３）中、Ｙは水素原子、又は置換基を有していても良く且つ不飽和基を含んでいても良い炭化水素基であり、複数のＹは互いに同一であっても良く、異なっていても良い。Ｚは置換基を有していても良い２価の炭化水素基（連結基）であり、複数のＺは互いに同一であっても良く、異なっていても良い。ａ、ｂ、ｃは平均値を表しそれぞれ独立に０〜７であり、ａ＋ｂ＋ｃは１．２〜７である。また、式（３）中のベンゼン環は表記していない置換基を有していても良い。） [4] The reactive resin composition according to [2], wherein the component (A) is a resin represented by the following formula (3).

(In the formula (3), Y is a hydrogen atom or a hydrocarbon group which may have a substituent and may contain an unsaturated group, and a plurality of Y may be the same as each other, Z may be a divalent hydrocarbon group (linking group) which may have a substituent, and a plurality of Z may be the same or different from each other. b and c each represent an average value and are each independently 0 to 7, and a + b + c is 1.2 to 7. In addition, the benzene ring in the formula (3) may have a substituent not described. good.)

[5] The reactive resin composition according to any one of [1] to [4], further comprising a pentafunctional or higher functional ethylenically unsaturated compound and a pigment.

[6] The reactive resin composition according to any one of [1] to [5], further comprising a substrate adhesion enhancer.

[7] The reactive resin composition according to any one of [1] to [6], wherein the component (B) is an oxime compound.

[8] The reactive resin composition according to any one of [1] to [7], which contains a novolak resin and / or a hydroxystyrene-based resin in addition to the component (A) resin. object.

（式（１）中、Ｘは、水素原子、或いはカルボキシル基及び／又は水酸基を有しさらにその他の置換基を有していても良い炭化水素基であり、複数のＸは互いに同一であっても良く、異なっていても良い。ｎは平均値を表し１．２〜７である。また、式（１）中のベンゼン環は表記していない置換基を有していても良い。） [9] A reactive resin composition for forming liquid crystal alignment control protrusions and / or spacers, or for simultaneously forming liquid crystal alignment control protrusions and spacers, the carboxyl group represented by the following formula (1) And / or a reactive resin composition containing an ink using a hydroxyl group-containing resin as a pigment dispersion resin.

(In the formula (1), X is a hydrogen atom or a hydrocarbon group having a carboxyl group and / or a hydroxyl group and further having another substituent, and a plurality of Xs are the same as each other. (N represents an average value and is 1.2 to 7. In addition, the benzene ring in formula (1) may have a substituent which is not shown).

[10] The reactive resin composition according to any one of [1] to [6], [8] and [9], wherein the component (B) is an o-quinonediazide compound.

[11] A color filter having liquid crystal alignment control protrusions and / or spacers formed using the reactive resin composition according to any one of [1] to [10].

[12] An image using a color filter having liquid crystal alignment control protrusions and / or spacers formed using the reactive resin composition according to any one of [1] to [10]. Display device.

  According to the reactive resin composition of the present invention, ribs and spacers can be formed in a preferable shape and have excellent electrical characteristics such as voltage holding ratio, residual potential, and electric capacity. When the spacer is formed, there is no adverse effect on the liquid crystal layer, and therefore, a liquid crystal display in which problems such as uneven display of liquid crystal and baking are improved and long-term new reliability is secured can be realized. Also, since it is difficult to adversely affect even if it is in direct contact with the liquid crystal, in addition to ribs and spacers, there are various applications such as omission of overcoat, unification of members, and efficiency by forming ribs and spacers together. The possibility can be expected.

  Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. These contents are not specified.

In the present invention, “(meth) acrylic acid” means that both acrylic acid and methacrylic acid are included, and “(meth) acrylate”, “(meth) acryloyl” and the like have the same meaning. . Moreover, what added "(poly)" in front of the monomer name means including both the said monomer and its polymer, and "(acid) anhydride", "(anhydrous) ... acid" Means to include both acids and their anhydrides.
In the present invention, the “total solid content” means all components except the solvent among the constituent components of the reactive resin composition of the present invention.

[Reactive resin composition]
First, the reactive resin composition of the present invention will be described in detail.
The reactive resin composition of the present invention is a reactive resin composition for forming liquid crystal alignment control protrusions and / or spacers, or for simultaneously forming liquid crystal alignment control protrusions and spacers. And (B) as a constituent component. In particular, the feature of the present invention is that (A) a resin having a skeleton of a condensate of a biphenyl compound and a phenol is used as a constituent component. .
(A) Resin having a condensate of a biphenyl compound and phenols as a skeleton (B) Photopolymerization initiator and / or photoacid generator

<(A) Resin having a skeleton of a condensate of a biphenyl compound and phenols>
(A) The biphenyl compound in the resin having a skeleton of a condensate of a biphenyl compound and phenols refers to all biphenyl compounds that can be condensed with phenols, for example, 4,4′-bischloromethylbiphenyl, 4, 4'-bischloromethyl-biphenyl-2-carboxylic acid, 4,4'-bischloromethyl-biphenyl-2,2'-dicarboxylic acid, 4,4'-bischloromethyl-2-methylbiphenyl, 4,4 '-Bischloromethyl-2,2'-dimethylbiphenyl and the like can be mentioned, but in addition, those having various substituents and reactive groups can be adopted. These biphenyl compounds can be used alone or in combination of two or more.

  On the other hand, phenols to be condensed with a biphenyl compound are aromatic compounds having one phenolic hydroxyl group in one molecule, and specific examples thereof include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, Various o-, m-, and p-isomers of alkylphenols such as t-butylphenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol and the like, or vinylphenol, allylphenol, propenylphenol, ethynylphenol Of various o-, m-, and p-isomers, cycloalkylphenols such as cyclopentylphenol, cyclohexylphenol, and cyclohexylresole, and phenylphenol. Conversion phenols and the like. These phenols can be used individually by 1 type or in combination of 2 or more types.

  These condensates of biphenyl compounds and phenols can be obtained, for example, by the method described in JP-A-2001-329051.

（式（１）中、Ｘは、水素原子、或いはカルボキシル基及び／又は水酸基を有しさらにその他の置換基を有していても良い炭化水素基であり、複数のＸは互いに同一であっても良く、異なっていても良い。ｎは平均値を表し１．２〜７である。また、式（１）中のベンゼン環は表記していない置換基を有していても良い。ここで、ベンゼン環とは、ビフェニレン基のベンゼン環とフェノキシ基（又はフェノキシ誘導体基）のベンゼン環の両方を指す。） In addition, it is preferable that the condensate (A) of the biphenyl compound and phenols of the present invention is a resin having a carboxyl group and / or a hydroxyl group represented by the following formula (1).

(In the formula (1), X is a hydrogen atom or a hydrocarbon group having a carboxyl group and / or a hydroxyl group and further having another substituent, and a plurality of Xs are the same as each other. N represents an average value and is 1.2 to 7. Further, the benzene ring in the formula (1) may have a substituent which is not described. The benzene ring refers to both the benzene ring of the biphenylene group and the benzene ring of the phenoxy group (or phenoxy derivative group).

（式（２）中、ｎは式（１）におけると同義である。また、式（２）中のベンゼン環は表記していない置換基を有していても良い。ここで、ベンゼン環とは、ビフェニレン基のベンゼン環とフェノキシ基のベンゼン環の両方を指す。） Here, one particularly preferable example of X in the formula (1) is a hydrogen atom. In this case, the resin represented by the formula (1) is represented by the following formula (2). Since this resin is excellent in electric characteristics and heat solubility, it is particularly preferable for the use of ribs for which the shape is desired to be secured by melt flow.

(In formula (2), n has the same meaning as in formula (1). Moreover, the benzene ring in formula (2) may have a substituent not shown. Refers to both the benzene ring of the biphenylene group and the benzene ring of the phenoxy group.)

（式（３）中、Ｙは水素原子、又は置換基を有していても良く且つ不飽和基を含んでいても良い炭化水素基であり、複数のＹは互いに同一であっても良く、異なっていても良い。Ｚは置換基を有していても良い２価の炭化水素基（連結基）であり、複数のＺは互いに同一であっても良く、異なっていても良い。ａ、ｂ、ｃは平均値を表しそれぞれ独立に０〜７であり、ａ＋ｂ＋ｃは１．２〜７である。また、式（３）中のベンゼン環は表記していない置換基を有していても良い。ここで、ベンゼン環とは、ビフェニレン基のベンゼン環とフェノキシ基（又はフェノキシ誘導体基）のベンゼン環の両方を指す。） Examples of preferable resin of the component (A) include those represented by the following formula (3).

(In the formula (3), Y is a hydrogen atom or a hydrocarbon group which may have a substituent and may contain an unsaturated group, and a plurality of Y may be the same as each other, Z may be a divalent hydrocarbon group (linking group) which may have a substituent, and a plurality of Z may be the same or different from each other. b and c each represent an average value and are each independently 0 to 7, and a + b + c is 1.2 to 7. In addition, the benzene ring in the formula (3) may have a substituent not described. Here, the benzene ring refers to both a benzene ring of a biphenylene group and a benzene ring of a phenoxy group (or phenoxy derivative group).

  Preferred examples of Y in the resin represented by formula (3) include alkyl groups such as methyl, ethyl, propyl, and butyl groups; alkenyl groups such as vinyl, allyl, propenyl, and isopropenyl groups; Aromatic groups such as phenyl group, styryl group, cinnamyl group and the like can be mentioned. Preferred examples of Z include alkylene groups such as methylene group, ethylene group, propylene group and cyclohexenylidene; alkenylidene groups such as ethenylidene group and propylidene group; phenylene group, methylphenylene group, dimethylphenylene group, trimethylphenylene group, Examples thereof include aromatic groups such as naphthylene group, carboxylphenylene group, and methoxyphenylene group. In particular, Y is a vinyl group or an isopropenyl group, Z is an ethylene group, a 4,5-cyclohexenylidene group, or a carboxylphenylene group, and a: b: c is 50 to 100: 0 to 50: 0 to 10. And a + b + c of 1.2 to 5 are excellent in the balance between reactivity and developability, and are preferable for image formation.

  In addition, when the reactive resin composition of the present invention includes a spacer application, the spacer is required to have compression characteristics. Therefore, when the resin itself is formed by photopolymerization, the double bond equivalent must be controlled. It becomes. In this case, for example, it is possible to design a resin by mixing an ethylenically unsaturated group and a highly elastic group with Y of the resin represented by the above formula (3). For example, this point is disclosed in JP-A-2005-55814. This is a big difference from the resin disclosed in the above.

（式中、Ｒ^１はハロゲン原子、水酸基、又は低級アルコキシ基を表す。） The resin represented by the above formula (2) can be obtained, for example, by subjecting a compound represented by the following formula (4) and a phenol to a condensation reaction in the presence of an acid catalyst.

(In the formula, R ¹ represents a halogen atom, a hydroxyl group, or a lower alkoxy group.)

In R ¹ of the above formula (4), a halogen atom is a chlorine atom, a bromine atom, etc., a lower alkyl group is a methyl group, an ethyl group, a t-butyl group, etc., and a lower alkoxy group is a methoxy group, an ethoxy group. Etc. are mentioned as preferable groups. Different compounds may be used in combination as the compound represented by the formula (4).

  On the other hand, the phenols to be condensed with the compound represented by the formula (4) are aromatic compounds having one phenolic hydroxyl group in one molecule, and specific examples thereof include phenol, cresol, ethylphenol, Various o-, m-, and p-isomers of alkylphenols such as n-propylphenol, isobutylphenol, t-butylphenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol and the like, or vinylphenol, Various o-, m-, and p-isomers of allylphenol, propenylphenol, and ethynylphenol, or cycloalkylphenol or phenylphenol, typically cyclopentylphenol, cyclohexylphenol, cyclohexylresole, etc. Substituted phenols such Lumpur and the like. These phenols can be used individually by 1 type or in combination of 2 or more types.

  When performing the said condensation reaction, Preferably the usage-amount of phenols is 0.5-20 mol with respect to 1 mol of compounds represented by Formula (4), Most preferably, it is 2-15 mol.

  In the above condensation reaction, it is preferable to use an acid catalyst, and various acid catalysts can be used, such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride, etc. 1 type or 2 types or more are preferable, and p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid are particularly preferable. Although the usage-amount of these acid catalysts is not specifically limited, It is preferable to use 0.1 to 30weight% with respect to the compound represented by Formula (4).

The condensation reaction can be performed in the absence of a solvent or in the presence of an organic solvent. In the case of using an organic solvent, specific examples thereof include one or more of toluene, xylene, methyl isobutyl ketone and the like.
The amount of the organic solvent used is preferably 50 to 300% by weight, particularly preferably 100 to 250% by weight, based on the total weight of the charged raw materials.
The reaction temperature is preferably in the range of 40 to 180 ° C., and the reaction time is preferably 1 to 8 hours.

After completion of the reaction, neutralization treatment or water washing treatment is performed to adjust the pH value of the product to 3-7, preferably 5-7. When performing the water washing treatment, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, sodium dihydrogen phosphate, diethylenetriamine, What is necessary is just to process using various basic substances, such as organic amines, such as a triethylenetetramine, aniline, and phenylenediamine, as a neutralizing agent.
In addition, the washing treatment may be performed according to a conventional method. For example, a method in which water in which the neutralizing agent is dissolved is added to the reaction mixture and the liquid separation extraction operation is repeated can be employed.

  After the neutralization treatment or the water washing treatment, the unreacted dihydroxybenzene (phenol) and the solvent are distilled off under reduced pressure heating to concentrate the product, and the compound represented by (2) above is obtained. Obtainable.

Moreover, although a well-known method is employable for manufacture of the compound represented by the said Formula (3), the following methods are mentioned, for example.
First, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added in advance or added to a dissolved mixture of the compound represented by formula (2) and an excess of epihalohydrin such as epichlorohydrin or epibromohydrin. The intermediate body which introduce | transduced the epoxy group is obtained by making it react at the temperature of 20-120 degreeC for 1 to 10 hours.

  In the reaction for obtaining the intermediate having the epoxy group introduced therein, the alkali metal hydroxide may be used as an aqueous solution, in which case the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system. A method may be employed in which water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, followed by liquid separation, water removal, and epihalohydrin being continuously returned to the reaction system.

  Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to a dissolved mixture of the compound represented by formula (2) and epihalohydrin, and 1 to 50-150 ° C. A solid or aqueous solution of an alkali metal hydroxide is added to the halohydrin etherified product of the compound represented by formula (2) obtained by reacting for 5 hours, and the reaction is again performed at a temperature of 20 to 120 ° C. for 1 to 10 hours. And dehydrohalogenation (ring closure).

  The amount of epihalohydrin used in such a reaction is usually 1 to 20 mol, preferably 2 to 10 mol, per 1 equivalent of the hydroxyl group of the compound represented by formula (2). Moreover, the usage-amount of an alkali metal hydroxide is 0.8-15 mol normally with respect to 1 equivalent of hydroxyl groups of the compound represented by Formula (2), Preferably it is 0.9-11 mol.

  Furthermore, in order to make the reaction proceed smoothly, the reaction may be carried out by adding an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide in addition to alcohols such as methanol and ethanol. When alcohols are used, the amount used is 2 to 20% by weight, preferably 4 to 15% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, the usage-amount is 5 to 100 weight% with respect to the quantity of an epihalohydrin, Preferably it is 10 to 90 weight%.

  After the reaction product of these epoxidation reactions is washed with water or without washing, epihalohydrin and other added solvents are removed under reduced pressure by heating at 110 to 250 ° C. and a pressure of 1.3 kPa (10 mmHg) or less. In addition, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved. The reaction can be carried out by adding an aqueous solution to ensure ring closure. In this case, the amount of the alkali metal hydroxide used is preferably 0.01 to 0.3 mol, particularly preferably 0.05 to 1 equivalent of the hydroxyl group of the compound represented by the formula (2) used for epoxidation. -0.2 mol. The reaction temperature is 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours. After completion of the reaction, the produced salt is removed by filtration, washing with water and the like, and further, a solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure.

  Next, this epoxy resin is reacted with a carboxylic acid compound. For this reaction, for example, the epoxy resin and carboxylic acid are mixed with a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium. Epoxy resin by reacting in a solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours using a quaternary ammonium salt such as chloride, tetraethylammonium chloride, benzyltriethylammonium chloride, pyridine, triphenylphosphine, etc. as a catalyst. Carboxylic acid can be added to.

  The amount of the catalyst used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight, based on the reaction raw material mixture (total of epoxy resin and carboxylic acid compound). In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine, etc.). Preferably it is 0.01 to 10 weight% with respect to a reaction raw material mixture, Most preferably, it is 0.1 to 5 weight%.

  The ratio of adding the carboxylic acid compound to the epoxy group of the epoxy resin is usually 90 to 100 mol%. Since the remaining epoxy group adversely affects the storage stability, the carboxylic acid compound is usually 0.8 to 1.5 equivalents, particularly 0.9 to 1.1 equivalents per 1 equivalent of epoxy group of the epoxy resin. It is preferable to carry out the reaction.

  The carboxylic acid compound used here is acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, benzoic acid, cinnamic acid, amino acid, crotonic acid, o-, m -, P-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, monocarboxylic acid such as cyano substitution, 2- (meth) acryloyloxyethyl succinic acid, 2-acryloyloxy Ethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxy Propyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropi Tetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipine Acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid, (meth) acrylic acid with ε-caprolactone, β A monomer obtained by adding a lactone such as propiolactone, γ-butyrolactone, δ-valerolactone, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate to (anhydrous) succinic acid, (Anhydrous) phthalic acid, maleic acid and other acids (anhydrides) added Body, and the like (meth) acrylic acid dimer. These can be used alone or in combination of two or more.

  Next, the resin represented by the formula (3) can be obtained by adding a polybasic acid and / or an anhydride thereof to the hydroxyl group of the reaction product of the epoxy resin and the carboxylic acid compound. As the polybasic acid and / or anhydride thereof used here, known ones can be used. Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, Dibasic carboxylic acids such as chlorendic acid, methyltetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic acid or their anhydrides; trimellitic acid, pyromellitic acid And polybasic carboxylic acids such as benzophenone tetracarboxylic acid and biphenyl tetracarboxylic acid, or anhydrides thereof. Among these, tetrahydrophthalic anhydride or succinic anhydride is preferable. These may be used alone or in combination of two or more.

  The addition rate of the polybasic acid and / or anhydride thereof is usually 10 to 100 mol%, preferably 20 to 100 mol%, more preferably of the hydroxyl group produced when the carboxylic acid compound is added to the epoxy resin. 30 to 100 mol%. If the addition rate is too small, the solubility may be insufficient or the adhesion to the substrate may be insufficient.

  As a method of adding a polybasic acid and / or an anhydride thereof to the hydroxyl group of the reaction product after adding a carboxylic acid compound to the aforementioned epoxy resin, a known method can be used. ) Can be obtained.

<Other resins>
In the reactive resin composition of the present invention, a resin having a condensate of a biphenyl compound of component (A) and a phenol as a skeleton can be mixed with any other resin. In this case, novolak resins, hydroxystyrene resins and the like are particularly preferable as the resin used in combination.

  As novolak resins, for example, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, propyl Phenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol, 4,4'-biphenyldiol, bisphenol-A, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, benzoic acid , 4-hydroxyphenylacetic acid, salicylic acid, phloroglucinol and other phenols in the presence of an acid catalyst, for example, formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde, propionaldehyde, benz It is a resin polycondensed with at least one of aldehydes such as aldehyde, salicylaldehyde, furfural, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

  The condensation reaction of the phenols and aldehydes is performed in the absence of a solvent or in a solvent. A resole resin polycondensed in the same manner can be used except that an alkali catalyst is used instead of the acid catalyst in the polycondensation of the novolak resin.

  The weight average molecular weight (hereinafter referred to as “Mw”) in terms of polystyrene by gel permeation chromatography (GPC) of the novolak resin is 1,000 to 20,000, preferably 1,000 to 10,000. Preferably it is 1,000-8,000. When Mw is less than 1,000, the electrical reliability is lowered, and when it exceeds 20,000, the developability is lowered.

  In order to enhance alkali solubility in the novolak resin, a carboxylic acid may be added to a part of the phenolic hydroxyl group. Examples of the carboxylic acid include oxalic acid, maleic acid, itaconic acid, phthalic acid, tetrahydro Phthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid 1 type, or 2 or more types, such as an acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, and those anhydrides are mentioned.

  Examples of the hydroxystyrene-based resin include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene, tetrahydroxystyrene, pentahydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy. Hydroxystyrenes such as -α-methylstyrene, p-hydroxy-α-methylstyrene, 2- (o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene, 2- (p-hydroxyphenyl) propylene ( These may have a halogen atom such as chlorine, bromine, iodine or fluorine, or an alkyl group having 1 to 4 carbon atoms as a substituent on the benzene ring. In addition, styrene, α-methylstyrene, etc. , (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, tricyclo [5.2.1.0] decan-8-yl (meth ) Polymerize one or more comonomers such as acrylate, glycidyl (meth) acrylate, and acrylic acid derivatives such as hydroxyphenyl (meth) acrylamide in the presence of a radical polymerization initiator or a cationic polymerization initiator. Examples thereof include homopolymers or copolymers of hydroxystyrenes.

  The Mw of the hydroxystyrene-based resin is 2,000 to 50,000, preferably 2,000 to 20,000. If the Mw is less than 2,000, the electrical reliability is lowered, and if it exceeds 50,000, the developability is lowered.

  For the hydroxystyrene resin, carboxylic acid may be added to a part of the phenolic hydroxyl group in order to enhance alkali solubility. Examples of the carboxylic acid include oxalic acid, maleic acid, itaconic acid, phthalic acid. Tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexa 1 type, or 2 or more types, such as hydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, and those anhydrides, are mentioned.

In the reactive resin composition of the present invention, when the resin of component (A) is mixed with the above novolak resins or hydroxystyrene resins, the weight ratio is the resin of component (A): (novolak resins and / or Or hydroxystyrene-based resin) = 0.5: 9.5 to 9.5: 0.5 is preferable, and 2: 8 to 8: 2 is particularly preferable.
By mixing and using novolak resins and hydroxystyrene resins in the component (A) resin, it is possible to further improve the seizure property and to adjust the shape, but the mixing ratio is too small. This improvement effect cannot be obtained sufficiently, and if it is too much, effects such as electrical characteristics and plate-making property by using the resin of component (A) cannot be sufficiently obtained in the present invention.

Moreover, alkali-soluble resin can also be used as resin other than resin of a component (A). The alkali-soluble resin is not particularly limited as long as it contains a carboxyl group or a hydroxyl group, and examples thereof include acrylic resins, urethane resins, and epoxy resins. These alkali-soluble resins can be used singly or in combination of two or more.
When other alkali-soluble resins are used, the ratio of use is preferably a weight ratio of resin of component (A): other alkali-soluble resins = 2: 8 to 9.9: 0.1, particularly preferably 3: 7-9.5: 0.5. By using other alkali-soluble resins for the resin of component (A), the compatibility and dispersibility with other components can be further increased, and performance such as compression properties can be provided. If the amount of the resin is too much, the effect of improving the electrical characteristics due to the use of the component (A) resin in the present invention cannot be sufficiently obtained.

<(B) Photopolymerization initiator and / or photoacid generator>
The photopolymerization initiator in the component (B) according to the present invention is a compound capable of generating radicals that polymerize ethylenically unsaturated groups by ultraviolet rays or heat.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine; Oxadiazole derivatives;
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) ) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, etc. An imidazole derivative of
Benzoin, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;

Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;
Benzanthrone derivatives;
Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2, -dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p- Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1, -trichloromethyl Acetophenone derivatives such as-(p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;

Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoropheny -1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluorophen-1-yl Di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-di-fluoro Feni-1-i , Di - cyclopentadienyl -Ti-2,6-di - fluoro-3- (pill-1-yl) - titanocene derivatives such as 1-yl;
2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-aminoalkylphenone compounds such as

  In addition, oxime derivatives (oxime compounds) are particularly effective in terms of sensitivity, and when the reactive resin composition of the present invention contains a phenolic hydroxyl group, it is particularly useful because it is disadvantageous in terms of sensitivity. .

Examples of the oxime derivatives include a compound containing a structural moiety represented by the general formula (5), and preferably an oxime ester compound represented by the general formula (6).

(In Formula (5), R ² is a C1-C20 heteroaryl group, a C2-C12 alkanoyl group, a C1-C20 heteroarylalkanoyl group, carbon which may be respectively substituted. C3-C25 alkenoyl group, C3-C8 cycloalkanoyl group, C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, C3-C20 heteroaryloxyoxy A carbonylalkanoyl group, or an aminocarbonyl group having 2 to 10 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or 7 to 20 carbon atoms The phenoxycarbonyl group of

(In formula (6), R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, Phenoxycarbonylalkyl group having 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, amino group having 0 to 20 carbon atoms, aminoalkyl group having 1 to 20 carbon atoms, carbon C2-C12 alkanoyl group, C3-C25 alkenoyl group, C3-C8 cycloalkanoyl group, C7-C20 benzoyl group, C1-C20 heteroaryloyl group, C2 10 alkoxycarbonyl group, show phenoxycarbonyl group having 7 to 20 carbon atoms, further ^{R 1a} is a form of a ring with R1 ' May be, the linkage is respectively may have a substituent group alkylene group having 1 to 10 carbon atoms, polyethylene group _{(- (CH = CH) r} -), Poriechiniren group (- (C △ C ) _R- : Δ is a triple bond) or a combination thereof (r is an integer of 0 to 3), and R1 ′ represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R ^2a is an optionally substituted heteroaryl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and an alkenoyl group having 3 to 25 carbon atoms. , A cycloalkanoyl group having 3 to 8 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxyoxycarbonylalkanoyl group having 3 to 20 carbon atoms, or a carbon number A 2-10 aminocarbonyl group, a C7-20 benzoyl group, a C1-C20 hetero aryloyl group, a C2-C10 alkoxycarbonyl group, or a C7-20 phenoxycarbonyl group is shown. )

  Specific examples of oxime derivatives include, but are not limited to, the following compounds.

  These oxime ester compounds are known per se, and are, for example, one of a series of compounds described in JP-A No. 2000-80068 and JP-A No. 2006-36750.

Said photoinitiator is used with an ethylenically unsaturated compound.
As used herein, an ethylenically unsaturated compound means a compound having at least one ethylenically unsaturated bond in the molecule, but it is polymerizable, crosslinkable, and a developer for exposed and non-exposed areas associated therewith. From the viewpoint that the difference in solubility can be expanded, the compound is preferably a compound having two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bond is derived from a (meth) acryloyloxy group (meta ) Acrylate compounds are more preferred.

  Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof. , (Meth) acrylonitrile, (meth) acrylamide, styrene and the like.

  The compounds having two or more ethylenically unsaturated bonds are typically esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, hydroxy (meth) acrylates. Examples include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.

Specific examples of esters of an unsaturated carboxylic acid and a polyhydroxy compound include the following compounds.
Reaction product of unsaturated carboxylic acid and sugar alcohol; specifically, sugar alcohol includes ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), trimethylene glycol, Examples include tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and the like.
Reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol; sugar alcohol is the same as above. Specific examples of the alkylene oxide adduct include an ethylene oxide adduct and a propylene oxide adduct.
Reaction product of unsaturated carboxylic acid and alcohol amine; specific examples of alcohol amines include diethanolamine and triethanolamine.

Specific esters of unsaturated carboxylic acid and polyhydroxy compound are as follows.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meta) ) Acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , And similar crotonate, isobutyl crotonate, maleate, itaconate, citraconate, etc.

  In addition, as esters of unsaturated carboxylic acid and polyhydroxy compound, unsaturated carboxylic acid and aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts These reactants can be mentioned. Specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc., and the unsaturated carboxylic acid as described above A reaction product with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, for example, di (meth) acrylate, tri (meth) acrylate, etc. of tris (2-hydroxyethyl) isocyanurate, Reaction product of unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound, for example, condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, condensate of (meth) acrylic acid, maleic acid and diethylene glycol , (Meth) acrylic acid, terephthalic acid and pentae Condensates of Suritoru include condensates of (meth) acrylic acid and adipic acid and butane diol and glycerol.

  As the (meth) acryloyloxy group-containing phosphates, those represented by the following general formulas (7), (8) and (9) are preferable.

（式（７），（８）及び（９）中、Ｒ^１０は水素原子又はメチル基を示し、ｐ及びｐ’は１〜２５の整数、ｑは１、２、又は３である。〕

(In the formulas (7), (8) and (9), R ¹⁰ represents a hydrogen atom or a methyl group, p and p ′ are integers of 1 to 25, and q is 1, 2 or 3.]

  Here, it is preferable that p and p ′ are 1 to 10, particularly 1 to 4, and specific examples thereof include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, Examples include (meth) acryloyloxyethylene glycol phosphate, and these may be used alone or as a mixture.

Examples of urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound include hydroxy (meth) acrylates such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetramethylolethane tri (meth) acrylate. ) Acrylate compound, aliphatic polyisocyanate such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptanetri Cycloaliphatic polyisocyanates such as isocyanate, 4,4-diphenylmethane diisocyanate, tris Aromatic polyisocyanates such as isocyanate phenyl) thiophosphate, heterocyclic polyisocyanates such as isocyanurate, a reaction product of a polyisocyanate compounds and the like.
Examples of such products include trade names “U-4HA”, “UA-306A”, “UA-MC340H”, “UA-MC340H”, “U6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

  Among these, a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable, and examples of the compound include pentaerythritol, poly A compound obtained by reacting a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate with a compound having 4 or more hydroxyl groups in one molecule such as glycerin, or ethylene glycol As a compound having two or more hydroxyl groups in one molecule, “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S-75E”, “Duranate 18H-70B”, etc. manufactured by Asahi Kasei Corporation Biuret type, same A compound having three or more isocyanate groups in one molecule such as adduct type such as “Duranate P-301-75E”, “Duranate E-402-90T” and “Duranate E-405-80T” is reacted. The compound obtained, or a compound obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like, a compound having 4 or more, preferably 6 or more isocyanate groups in one molecule, such as Asahi Kasei Kogyo “Duranate ME20-100”, pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. 1 or more hydroxyl groups and 2 in one molecule Above, can preferably be obtained by a compound having three or more (meth) acryloyloxy group, it is reacted.

  Examples of epoxy (meth) acrylates of (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound include (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, and (poly) Ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene Glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether Aliphatic polyepoxy compounds such as, phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds, etc. Aromatic polyepoxy compounds, sorbitan polyglycidyl ether, triglycidyl isocyanurate, heterocyclic polyepoxy compounds such as triglycidyl tris (2-hydroxyethyl) isocyanurate, and reactants with polyepoxy compounds such as .

  Other ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, ether bonds Thioether bond-containing compounds whose crosslinking rate has been improved by sulfurizing the ether bonds of the ethylenically unsaturated compound with phosphorous pentasulfide and changing to thioether bonds, and for example, Japanese Patent No. 3164407 and JP-A-9- The polyfunctional (meth) acrylate compound and silica sol having a particle diameter of 5 to 30 nm (for example, isopropanol-dispersed organosilica sol (“IPA-ST” manufactured by Nissan Chemical Co., Ltd.)), methyl ethyl ketone-dispersed organosilica sol (Nissan Chemical) "MEK-S" ”), Methyl isobutyl ketone-dispersed organosilica sol (“ MIBK-ST ”manufactured by Nissan Chemical Co., Ltd.), etc.] and the like, and the like, and the like, by using an isocyanate group or a mercapto group-containing silane coupling agent. Examples thereof include compounds in which the strength and heat resistance as a cured product are improved by reacting and bonding silica sol through a silane coupling agent.

  The above ethylenically unsaturated compounds may be used alone or in combination of two or more.

  In the present invention, as the ethylenically unsaturated compound, ester (meth) acrylates or urethane (meth) acrylates are preferable, and among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like. Those having 5 or more functional groups are particularly preferred.

  Moreover, when using a photoinitiator as a component (B) component, the sensitizing dye according to the wavelength of an image exposure light source can be mix | blended as needed for the purpose of improving a sensitivity. Examples of these sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and coumarins having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335. Dyes, 3-ketocoumarin compounds described in JP-A-3-239703, JP-A-5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, JP-A 54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403 JP-A-2-69, JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, JP-A-4-288. Dyes having a dialkyl aminobenzene skeleton as described in 18 JP can be exemplified. These can be used alone or in combination of two or more.

The other photoacid generator of the component (B) according to the present invention is a compound capable of generating an acid by ultraviolet rays, and preferably contains at least an o-quinonediazide compound, preferably a naphthoquinonediazide derivative.
The naphthoquinonediazide derivative may be a monofunctional compound, a bifunctional or higher compound, or a mixture thereof.

  The monofunctional naphthoquinonediazide derivative is preferably an ester compound obtained by reacting naphthoquinone-4-sulfonic acid chloride or naphthoquinone-5-sulfonic acid chloride with a substituted phenol. The bifunctional or higher naphthoquinonediazide derivative is preferably an ester compound obtained by reacting naphthoquinone-4-sulfonic acid chloride or naphthoquinone-5-sulfonic acid chloride with a compound having a plurality of phenolic hydroxyl groups.

  Examples of the compound having a plurality of phenolic hydroxyl groups include polyphenols such as bisphenols, trisphenols and tetraquinosphenols; polyfunctional phenols such as dihydroxybenzene and trihydroxybenzene; bis-type or tris-type dihydroxybenzene or Trihydroxybenzene, asymmetric polynuclear phenol, a mixture thereof, and the like are preferable.

  Specific examples of the compound having a phenolic hydroxyl group include, for example, 4-t-butylphenol, 4-isoamylphenol, 4-t-octylphenol, 2-isopropyl-5-methylphenol, 2-acetylphenol, and 4-hydroxybenzophenone. , 3-chlorophenol, 4-benzyloxycarbonylphenol, 4-dodecylphenol, resorcinol, 4- (1-methyl-1-phenylethyl) -1,3-benzenediol, chloroglucinol, 4,4′-dihydroxy Benzophenone, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-4-hydroxyphenyl) methane, 2,3,4,4′- Tetrahydroxybenzophenone, 4,4 ' [(4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], and the like.

Specific examples of the naphthoquinonediazide derivative include, for example, 4′-t-octylphenylnaphthoquinonediazide-4-sulfonate, 4′-t-octylphenylnaphthoquinonediazide-5-sulfonate, 4′-benzoylphenylnaphthoquinonediazide-5 Examples include sulfonate, a reaction product of 2,3,4,4′-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid chloride.
These may be used alone or in combination of two or more.

<Ratio of component (A) and component (B)>
In the reactive resin composition of the present invention, the blending ratio of the component (A) and the component (B) varies depending on the type of the component used, but is preferably the following blending ratio by weight ratio.
When component (B) is a photopolymerization initiator such as an oxime compound, component (A): component (B) is usually 99.9: 0.1 to 65:35, preferably 99: 1 to 75:25. It is. When a resin other than component (A) is used, (component (A) + resin other than component (A)): component (B) is 99.9 to 0.1: 65: 35, preferably 99: 1-75: 25. If the amount of the component (B) is too small, sufficient sensitivity cannot be obtained. If the amount is too large, problems occur in developability and storage stability.
When component (B) is a photoacid generator such as an o-quinonediazide compound, component (A): component (B) is usually 97: 3 to 30:70, preferably 90:10 to 50:50. . If the amount of the component (B) is too small, the effect is not obtained, and if it is too large, the platemaking property is lowered.
When a sensitizing dye is added, the content of the sensitizing dye in the reactive resin composition is 0.1 to 10% by weight, preferably 0.2 to 5% by weight. If it is less than this, the sensitizing effect will not be obtained, and if it is too much, the developability will be lowered.

<Board adhesion enhancer>
The reactive resin composition of the present invention preferably contains a substrate adhesion enhancing agent in order to sufficiently adhere thin rib lines and dots.
As the substrate adhesion enhancer, a compound containing a nitrogen atom, a phosphoric acid group-containing compound, a silane coupling agent or the like is preferable. Examples of the compound containing a nitrogen atom include diamines (adhesion enhancement described in JP-A No. 11-184080). Agents, others) and azoles are preferred. Of these, azoles are preferable, and imidazoles (adhesion enhancers described in JP-A-9-236923, etc.), benzimidazoles, and benzotriazoles (adhesion enhancers described in JP-A 2000-171968, etc.) are particularly preferable. And benzimidazoles are most preferred. Among these, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, 2 are less likely to cause fogging and greatly improve adhesion. -Aminoimidazole is preferable, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, and imidazole are particularly preferable.

  As the phosphoric acid group-containing compound, (meth) acryloyloxy group-containing phosphates that also function as an ethylenically unsaturated compound are preferable, and those represented by the following general formulas (7), (8), and (9) are preferable. .

（式（７），（８）及び（９）中、Ｒ^１０は水素原子又はメチル基を示し、ｐ及びｐ’は１〜２５の整数、ｑは１、２、又は３である。〕

(In the formulas (7), (8) and (9), R ¹⁰ represents a hydrogen atom or a methyl group, p and p ′ are integers of 1 to 25, and q is 1, 2 or 3.]

  Here, it is preferable that p and p ′ are 1 to 10, particularly 1 to 4, and specific examples thereof include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, Examples include (meth) acryloyloxyethylene glycol phosphate, and these may be used alone or as a mixture.

  Various types of silane coupling agents such as epoxy, methacrylic, amino and the like can be used, and epoxy silane coupling agents are particularly preferable.

  When blending these substrate adhesion enhancing agents, the blending ratio varies depending on the type of substrate adhesion enhancing agent used, but is 0.05 to 10% by weight, particularly 0.5 to 5%, based on the total reactive resin composition. It is preferable to set it as weight%.

<Color material>
The reactive resin composition of the present invention may contain a coloring material such as a pigment. In that case, the resin of the component (A) according to the present invention can also function as a dispersion resin. That is, the reactive resin composition of the present invention may contain an ink using a resin having a carboxyl group and / or a hydroxyl group represented by the formula (1) as a pigment dispersion resin.
In that case, particularly as the resin of component (A), Y in the formula (3) does not have an ethylenically unsaturated group, the molar ratio of a in a + b + c is 80% or more, and the acid value is 100 to 200 mg-KOH. / G is particularly preferable in view of dispersibility.
The dispersion resin is not limited to the resin of the component (A), and can be appropriately used as necessary.

  As a pigment when used in a mixture with the reactive resin composition of the present invention, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment are used. be able to. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. Terms such as “CI Pigment Red 2” mentioned below mean the color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

  The black color material may be a single black color material, or may be a mixture of red, green, blue and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable to use the pigment dispersed in an average particle size of 1 μm or less, preferably 0.5 μm or less.

  Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

  In addition, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.

  Among these, carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.

  Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B

  Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, C lor Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

  Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8

  Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000.

  As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.

  In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used as the pigment.

  These various pigments can also be used in combination of, for example, chromaticity adjustment.

  The average particle size of these various inorganic and organic pigments is usually 1 μm, preferably 0.5 μm or less, more preferably 0.25 μm or less.

  Examples of dyes that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.

  Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  When the coloring material is used in the reactive resin composition of the present invention, the ratio of the coloring material such as a pigment can be selected in the range of 1 to 50% by weight in the total solid content of the reactive resin composition. In this range, 10 to 40% by weight is more preferable, and 20 to 40% by weight is particularly preferable. If the proportion of the color material is too small, the required light shielding properties cannot be ensured in the case of a light shielding rib or the like. Conversely, if the proportion of the color material is too large, a sufficient rib shape may not be obtained.

  In addition, when the reactive resin composition of this invention contains a pigment, you may add a pigment derivative etc. for the improvement of the dispersibility of a pigment, and the improvement of dispersion stability. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Derivatives such as quinophthalone are preferable, among which quinophthalone is preferable. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton. Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These pigment derivatives can be used alone or in combination of two or more.

  The addition amount of the pigment derivative is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight or less, more preferably 0.1 to 10% by weight, still more preferably 0.1 to 5% by weight based on the pigment. % Or less.

  When the reactive resin composition of the present invention contains a pigment, it is preferable to use a pigment dispersant and / or a dispersion aid together in order to improve the dispersibility and dispersion stability of the pigment. Among them, it is particularly preferable to use a polymer dispersant as the pigment dispersant because it is excellent in dispersion stability with time. Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester. And the like, and the like. Specific examples of such a dispersant include trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbik (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), and SOLPERSE (manufactured by Geneca) ), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.) and the like. These dispersants can be used singly or in combination of two or more.

  The content of the pigment dispersant and / or the dispersion aid is usually 50% by weight or less, preferably 30% by weight or less in the solid content of the reactive resin composition.

<Other ingredients>
The reactive resin composition of the present invention includes (A) a resin having a skeleton of a condensate of a biphenyl compound and phenols, and (B) a photopolymerization initiator and / or a photoacid generator as constituent components. Although not particularly limited, in addition to the components listed above, further include melamine derivatives, surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protective agents, development improvers, crosslinking agents, etc. You can leave.

The melamine derivative undergoes dehydration or demethanol condensation reaction between the phenol group-containing resin and the methylol group or methoxymethyl group of the melamine derivative by the action of an acid generated from the photoacid generator. For this reason, the resin can be subjected to a crosslinking reaction with a melamine derivative. Such a melamine derivative may be a compound having a methylol group or a methoxymethyl group. Among these melamine derivatives, those having high solubility, particularly solubility in a solvent are preferable, for example, di-, tri-, tetra-, penta-, hexa-methylol melamine, or di-, tri-, Examples include, but are not limited to, melamine compounds such as tetra-, penta-, and hexa-methoxymethyl melamine, or melamine resins obtained by reacting these compounds with formaldehyde and the like. You may use these individually by 1 type or in combination of 2 or more types.
0.1-20 weight part is preferable with respect to 100 weight part of solid content of a reactive resin composition, and, as for the quantity at the time of using a melamine derivative, Most preferably, it is 1-10 weight part.

Various types of surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants, but nonionic surfactants are used because they are unlikely to adversely affect various properties. It is preferable to use it.
The blending ratio of the surfactant is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to 0. 0% by weight based on the total solid content in the reactive resin composition. It is in the range of 5% by weight, most preferably 0.03-0.3% by weight.

As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used.
The blending ratio of the thermal polymerization inhibitor is preferably in the range of 0 to 2% by weight with respect to the total solid content in the reaction resin composition.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin.
The blending ratio of these plasticizers is preferably in the range of 5% by weight or less with respect to the total solid content in the reactive resin composition.

  You may add crosslinking agents, such as a melamine, to the reactive resin composition of this invention. Examples of the crosslinking agent include melamine or guanamine compounds, and more specifically, for example, melamine or guanamine compounds represented by the following formula (14).

〔式中、Ｒ^１１は基−ＮＲ^１６Ｒ^１７又はアリール基を表し、Ｒ^１１が基−ＮＲ^１６Ｒ^１７の場合はＲ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６及びＲ^１７のうちの一つが、そしてＲ^１１がアリール基の場合はＲ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５のうちの一つが、基−ＣＨ_２ＯＲ^１８を表し、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６及びＲ^１７の残りは互いに独立に、水素又は基−ＣＨ_２ＯＲ^１８を表す。ここで、Ｒ^１８は水素又はアルキル基を表す。〕

^{Wherein, R 11} represents a group ^-NR 16 ^{R 17} or an aryl ^group, if ^{R 11} is a group ^-NR 16 ^{R 17} of ^{R 12, R 13, R 14} , R 15, R 16 and ^{R 17} And when R ¹¹ is an aryl group, one of R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represents the group —CH ₂ OR ¹⁸ , and R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and the remainder of R ¹⁷ independently of one another represent hydrogen or the group —CH ₂ OR ¹⁸ . Here, R ¹⁸ represents hydrogen or an alkyl group. ]

Here, the aryl group of R ¹¹ is typically a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and these phenyl group and naphthyl group have substituents such as an alkyl group, an alkoxy group and a halogen. It may be bonded. The alkyl group and alkoxy group as the substituent can each have about 1 to 6 carbon atoms. Among the above, the alkyl group represented by R ¹⁸ is generally an alkyl group having 1 to 6 carbon atoms, particularly a methyl group or an ethyl group, particularly a methyl group.

  Melamine compounds corresponding to the above formula (14), that is, compounds represented by the following formula (15) include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetramethoxy. Methyl melamine, hexaethoxymethyl melamine and the like are included.

〔式中、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６及びＲ^１７は互いに独立に、水素又は基−ＣＨ_２ＯＲ^１８を表す。ここで、Ｒ^１８は水素又はアルキル基を表す。〕

[Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ independently of one another represent hydrogen or the group —CH ₂ OR ¹⁸ . Here, R ¹⁸ represents hydrogen or an alkyl group. ]

Examples of guanamine compounds corresponding to formula (14), that is, compounds in which R ¹¹ in formula (14) is an aryl group include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine, and the like. Is included.

Furthermore, the following compounds are also included in the crosslinking agent having a methylol group or a methylol alkyl ether group, and these can also be used.
2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3 , 5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3,5-bis (hydroxymethyl) perhydro-1,3,5- Oxadiazin-4-one (commonly called dimethyloluron) or a dimethyl ether thereof, tetramethylol glyoxal diurein or a tetramethyl ether thereof.

  These crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type.

  When the crosslinking agent is used in the reactive resin composition of the present invention, the addition amount can be in the range of 1 to 60 parts by weight, preferably 5 to 50 parts by weight with respect to 100 parts by weight of the phenol-containing resin. Part. When the amount of the cross-linking agent is less than 1 part by weight, sufficient curability cannot be obtained. On the other hand, when the amount of the melamine is more than 60 parts by weight, the heat flow is difficult to occur, so that the shape control becomes difficult.

<Solvent>
Each component contained in the reactive resin composition of the present invention shown above is usually dissolved or dispersed in a solvent and used as a reactive resin composition solution.

  Examples of the solvent used here include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, soak solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methyl Ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-ethoxy Methyl propionate, 3-ethoxypropyl Ethyl lopionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether , Propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate and the like. These solvents may be used alone or in combination of two or more.

  In the reactive resin composition of the present invention, the content of the solvent is 90% by weight or less, 60% by weight or more, particularly 70% by weight or more from the viewpoint of ease of application during coating film formation and film thickness control. Preferably there is.

Since the reactive resin composition of the present invention has excellent electrical properties, it is useful as a material for forming a member close to the liquid crystal phase in addition to a material for forming a liquid crystal alignment control protrusion (rib) and spacer. It is.
That is, a voltage is applied to the liquid crystal layer by turning on and off the applied signal, and it is required to hold the applied voltage until the next writing, but there is a problem in the voltage holding ability of the liquid crystal layer Therefore, display defects such as flickering occur in the displayed image.
In general, the deterioration of the voltage holding ratio is caused by the entry of mobile ions into the liquid crystal layer or the low resistance of the members surrounding the liquid crystal layer. In particular, severe electrical characteristics are required for the contact or extremely adjacent members.

[Liquid Crystal Display (Panel)]
Below, the method to manufacture a liquid crystal display device (panel) using the reactive resin composition of this invention is demonstrated.
In a liquid crystal display device, an alignment film is formed on a color filter on which liquid crystal alignment control protrusions (ribs) and spacers are formed, and then bonded to a counter substrate to form a liquid crystal cell, and liquid crystal is injected into the formed liquid crystal cell. And it is manufactured by connecting to the counter electrode. In such a liquid crystal display device, liquid crystal alignment control protrusions (ribs) and / or spacers can be formed using the reactive resin composition of the present invention. When using a bead type spacer as the spacer, the spacer is applied after the alignment film is formed. The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and a curing process is performed by thermal baking. The thickness of the alignment film is usually several tens of nm.

  Formation of the liquid crystal alignment control protrusion (rib) using the reactive resin composition of the present invention is performed, for example, as follows.

  In forming the liquid crystal alignment control protrusions (ribs), first, a black matrix obtained by the method described in JP-A-2003-33011 and a color filter of red, blue, and green are provided, and further, An electrode such as ITO having a thickness of 150 nm is vapor-deposited (the electrode is not limited thereto). A transparent substrate having a thickness of usually 0.1 to 2 mm is prepared, and the above-described reactive resin composition solution of the present invention is applied to the transparent substrate. After coating and then drying, image exposure is performed.

  The aforementioned reactive resin composition solution of the present invention can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. In particular, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering to the spin coating method, and the generation of foreign matter is suppressed. To preferred.

  The coating film after the photosensitive colored resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying conditions are usually selected in the range of 15 to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.

  The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, when the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.

  Image exposure is performed by superimposing a matrix pattern on the coating film of the reactive resin composition of the present invention, and irradiating an ultraviolet or visible light source through this matrix risk pattern. Examples of the light source used for the above image exposure include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a lamp light source such as a carbon arc, a fluorescent lamp, Examples thereof include laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. When irradiating and using light of a specific wavelength, an optical filter can be used.

  After the exposure, in the case of a negative photosensitive composition, the unexposed uncured part is removed, and in the case of a positive photosensitive composition, the exposed alkali-solubilized part is removed by development, whereby the pixel is removed. Form. Development can be performed using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. The developer can contain an organic solvent, a buffering agent, and a complexing agent.

  Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, phosphorus Inorganic alkaline compounds such as potassium acid, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or Trimethylamine, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Yes And alkali compounds. These alkaline compounds may be used as a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzenes. Examples thereof include anionic surfactants such as sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate salts, and amphoteric surfactants such as alkylbetaines and amino acids.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used by mixing with water.

  The temperature of development processing is 10-50 degreeC normally, Preferably it is 15-45 degreeC, More preferably, it is 20-40 degreeC. Further, the developing method may be any of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like. Usually, an image obtained after development is required to have a fine line reproducibility with a width of 5 to 20 μm, and there is a tendency that a finer fine line reproducibility is required due to a demand for a high-quality display.

  The reactive resin composition of the present invention is usually 150 ° C. or higher, preferably 180 ° C. for the purpose of obtaining a shape necessary for liquid crystal alignment control protrusions and spacers after development and obtaining sufficient electric reliability. ℃ or higher, more preferably 200 ℃ or higher, usually 400 ℃ or lower, preferably 300 ℃ or lower, more preferably 280 ℃ or lower, and usually 10 minutes or longer, preferably 15 minutes or longer, more preferably 20 minutes or longer, usually The heat treatment is performed for 120 minutes or less, preferably 60 minutes or less, more preferably 40 minutes or less.

The liquid crystal alignment control protrusion formed as described above has an arch shape with a bottom width of usually 0.5 to 20 μm, preferably 3 to 17 μm, and a height of usually 0.2 to 5 μm, preferably 0.5 to 3 μm. The dome shape is preferable, and the angle with the substrate surface is usually 10 to 40 °, preferably 15 to 35 °. Meanwhile, the spacer height is usually 0.5 to 10 [mu] m, preferably 1 to 9 m, the bottom area is usually 10 to 300 [mu] m ^2, preferably columnar shape of 40 to 200 [mu] m ^2, the angle between the substrate surface normal 15 It is -110 degrees, Preferably it is 20-90 degrees.

  In the case of batch formation in which the liquid crystal alignment control protrusions and spacers are formed simultaneously with the same reactive resin composition, it is necessary to form different heights with a single coating (with the same coating film thickness). is there. For this purpose, various methods as proposed so far can be used. For example, a photomask used for exposure has a pattern with different transmittance and transmission wavelength, a step in exposure illuminance is made by adjusting the opening width of the mask, exposure is performed from both the front and back sides, and masks with different patterns multiple times The method of exposing using, etc. is mentioned.

  The liquid crystal alignment control protrusions (ribs) and spacers thus obtained may be transparent or colored depending on the application, but the light passing through the ribs is scattered because it is scattered. For example, when high contrast is required, such as a TV, a light shielding rib is required. When such a light shielding rib is formed, a coloring material such as the aforementioned pigment is mixed with the reactive resin composition and used.

On the other hand, as the spacer of the liquid crystal display device, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and usually a spacer of 2 to 8 μm is preferable.
In recent years, the use of a photo spacer formed by a photolithography method using a reactive resin has been increasing, but this spacer (photo spacer) and a rib are formed of the same reactive resin composition, and further, By forming them simultaneously at the same time, significant rationalization of materials and processes (processing time and place) can be expected. The reactive resin composition of the present invention is also in anticipation of this, and in particular, since the spacer is required to have compression characteristics, it is necessary to control the double bond equivalent when the resin itself is formed or formed by photopolymerization. It becomes. In that case, for example, a design in which an ethylenically unsaturated group and a highly elastic group are introduced into Y of the resin represented by the formula (3) becomes possible.

As the counter substrate of the liquid crystal display device, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable. The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed. The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of decompression in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. . The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower. The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The reactive resin composition of the present invention is basically intended for rib use, and the rib is used for the MVA method using a vertical alignment type liquid crystal, but the type of liquid crystal is not particularly limited, Conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known, but any of them may be used.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
The structural components of the reactive resin compositions used in the following examples and comparative examples are as follows.

<Photopolymerization initiator-1>

<Photopolymerization initiator-2>

<Photopolymerization initiator-3 (thermal crosslinking initiator)>

<Base adhesion enhancer>

<Crosslinking agent>

<Ink-1>
A reaction vessel was charged with 35 parts by weight of propylene glycol monomethyl ether acetate, 8.8 parts by weight of 1-methoxy-2-propanol, and 1.5 parts by weight of an azo polymerization initiator (“V-59” manufactured by Wako Pure Chemical Industries, Ltd.). In a nitrogen atmosphere, the temperature was raised to 80 ° C., 10.5 parts by weight of benzyl methacrylate, 7.5 parts by weight of methyl methacrylate, and 11.9 parts by weight of methacrylic acid were added dropwise over 2 hours, and further 4 hours. Stirring was performed to obtain Dispersing Resin-1. The average molecular weight of dispersion resin-1 by GPC was 12000 in terms of polystyrene, and neutralization titration with KOH gave an acid value of 120 mg-KOH / g.
Next, C.I. I. Pigment Red 254, 52 parts by weight, C.I. I. Pigment Blue 156, 37 parts by weight, C.I. I. 11 parts by weight of Pigment Violet 23, 25 parts by weight of the dispersant “DisperBYK-161” (manufactured by Big Chemie), 30 parts by weight of the above-mentioned Dispersing Resin-1 in solids, and a dispersant of propylene glycol monomethyl ether acetate And 620 parts by weight including those derived from the dispersion resin. Here, zirconia beads (0.5 mm diameter) of 3 times the total weight were mixed, filled in a stainless steel container, and dispersed for 6 hours with a paint shaker to prepare ink-1.

<Resin-1>
“ZCR-1569H” manufactured by Nippon Kayaku Co., Ltd. (Mw = 4000 to 5000, acid value = 100 mg-KOH / g)

<Resin-2>
It was synthesized by the following method.
“NC-3000H” (epoxy equivalent 280 to 300) 400 g, Nippon Kayaku Co., Ltd., 51 g of acrylic acid, 42 g of glacial acetic acid, 0.3 g of p-methoxyphenol, 5 g of triphenylphosphine, and 264 g of propylene glycol monomethyl ether acetate The reaction vessel was charged and stirred at 95 ° C. until the acid value was 3 mg-KOH / g or less. It took 9 hours for the acid value to reach the target (acid value 2.2 mg-KOH / g). Next, 151 g of tetrahydrophthalic anhydride was further added and reacted at 95 ° C. for 4 hours to obtain a resin-2 solution having an acid value of 100 mg-KOH / g and a weight average molecular weight of 3600 in terms of polystyrene measured by GPC.

<Resin-3>
m-cresol novolak resin (Mw = 5000)

<Resin-4>

<Resin-5>
“ZAR-2001H” manufactured by Nippon Kayaku Co., Ltd. (bisphenol A type, Epoac resin; Mw = 4000 to 5000, acid value = 100 mg-KOH / g)

<Resin-6>
“ZCR-1599H” manufactured by Nippon Kayaku Co., Ltd. (Naphthalene novolak type, Epoac resin; Mw = 4000 to 5000, acid value = 100 mg-KOH / g)

<Ethylenically unsaturated compound>

<Solvent>
Propylene glycol monomethyl ether acetate (PGMEA)

[Examples 1 to 3, Comparative Examples 1 to 5]
The components shown in Table 1 were mixed well with the formulation shown in Table 1, reactive resin composition solutions 1 to 8 were prepared, and the voltage holding ratio (VHR) was evaluated by the following method. It was shown to.

<Evaluation of voltage holding ratio (VHR)>
An electrode substrate A in which an ITO film is formed on one entire surface of a 2.5 cm square alkali-free glass substrate (AN-100 manufactured by Asahi Glass Co., Ltd.) and a 2 mm width at the center of one surface of the 2.5 cm square glass substrate. An electrode substrate B on which a 1 cm square ITO film with a lead-out electrode connected was prepared.
Each reactive resin composition solution was applied onto the electrode substrate A, vacuum-dried for 1 minute, and then pre-baked at 80 ° C. for 3 minutes on a hot plate to obtain a coating film having a dry film thickness of 1.9 μm. Thereafter, the entire surface was subjected to image exposure using 3 kW high-pressure mercury under exposure conditions of 80 mJ / cm ² . Next, 0.16 wt% sodium carbonate, 0.046 wt% sodium bicarbonate, 0.4 wt% nonionic surfactant (Adecatol PC-8), and 0.1 wt% propylene glycol. The developer comprising the aqueous solution contained was subjected to shower development at 26 ° C. and a water pressure of 0.1 MPa for 60 seconds, and then the development was stopped with pure water and rinsed with a water spray. The glass substrate thus image-formed was post-baked at 230 ° C. for 30 minutes to obtain a glass substrate having a resist on the entire surface.
On the other hand, after applying an epoxy resin sealant containing silica beads having a diameter of 5 μm on the outer periphery of the electrode substrate B using a dispenser, the outer edge of the electrode substrate A is shifted 3 mm from the surface to which the resist is applied. In the hot air circulating furnace, they were heated at 180 ° C. for 2 hours while facing each other and pressed.
Liquid crystal (MLC-6846-000 manufactured by Merck Japan Co., Ltd.) was injected into the empty cell thus obtained, and the periphery was sealed with a UV curable sealant to complete a voltage holding ratio liquid crystal cell.
After annealing the liquid crystal cell (heating at 105 ° C. for 2.5 hours in a hot air circulating furnace), a pulse voltage having the frequency shown in Table 1 is applied to the electrode substrates A and B at a voltage of 5 V and an application time of 16.67 msec, The voltage was applied under the condition of a span of 500 msec, and the voltage holding ratio was measured with “VHR-1” manufactured by Toyo Corporation.

  As shown in Table 1, it can be seen that the resin layer formed using the reactive resin composition of the present invention has almost no adverse effect on the voltage holding ratio of the liquid crystal even in the state where the liquid crystal is in direct contact. Therefore, it is very preferable as a material for forming liquid crystal alignment control protrusions (ribs) and spacers that are used by being arranged at a position very close to the liquid crystal, that is, only the alignment film at the boundary.

Claims (12)

A reactive resin composition for forming liquid crystal alignment control protrusions and / or spacers, or for simultaneously forming liquid crystal alignment control protrusions and spacers, comprising the following (A) and (B) as constituent components A reactive resin composition characterized by the above.
(A) Resin having a skeleton of a condensate of a biphenyl compound and phenols (B) Photopolymerization initiator and / or photoacid generator A reactive resin composition for forming liquid crystal alignment control protrusions and / or spacers, or for simultaneously forming liquid crystal alignment control protrusions and spacers, comprising the following (A) and (B) as constituent components A reactive resin composition characterized by the above.
(A) Resin having a carboxyl group and / or a hydroxyl group represented by the following formula (1) (B) Photopolymerization initiator and / or photoacid generator

(In the formula (1), X is a hydrogen atom or a hydrocarbon group having a carboxyl group and / or a hydroxyl group and further having another substituent, and a plurality of Xs are the same as each other. (N represents an average value and is 1.2 to 7. In addition, the benzene ring in formula (1) may have a substituent which is not shown). The reactive resin composition according to claim 2, wherein the component (A) is a novolak resin represented by the following formula (2).

(In formula (2), n has the same meaning as in formula (1). Moreover, the benzene ring in formula (2) may have a substituent not shown.) The reactive resin composition according to claim 2, wherein the component (A) is a resin represented by the following formula (3).

(In the formula (3), Y is a hydrogen atom or a hydrocarbon group which may have a substituent and may contain an unsaturated group, and a plurality of Y may be the same as each other, Z may be a divalent hydrocarbon group (linking group) which may have a substituent, and a plurality of Z may be the same or different from each other. b and c each represent an average value and are each independently 0 to 7, and a + b + c is 1.2 to 7. In addition, the benzene ring in the formula (3) may have a substituent not described. good.)   The reactive resin composition according to any one of claims 1 to 4, further comprising a pentafunctional or higher functional ethylenically unsaturated compound and a pigment.   The reactive resin composition according to claim 1, further comprising a substrate adhesion enhancer.   The reactive resin composition according to any one of claims 1 to 6, wherein the component (B) is an oxime compound.   The reactive resin composition according to any one of claims 1 to 7, further comprising a novolak resin and / or a hydroxystyrene-based resin in addition to the component (A) resin. A reactive resin composition for forming liquid crystal alignment control protrusions and / or spacers, or for simultaneously forming liquid crystal alignment control protrusions and spacers, which is represented by the following formula (1) and / or A reactive resin composition comprising an ink using a resin having a hydroxyl group as a pigment dispersion resin.

(In the formula (1), X is a hydrogen atom or a hydrocarbon group having a carboxyl group and / or a hydroxyl group and further having another substituent, and a plurality of Xs are the same as each other. (N represents an average value and is 1.2 to 7. In addition, the benzene ring in formula (1) may have a substituent which is not shown).   The reactive resin composition according to any one of claims 1 to 6, 8, and 9, wherein the component (B) is an o-quinonediazide compound.   A color filter comprising liquid crystal alignment control protrusions and / or spacers formed using the reactive resin composition according to claim 1.   An image display device comprising a color filter having liquid crystal alignment control protrusions and / or spacers formed using the reactive resin composition according to claim 1.